Process for treating and rectifying vapors



April 2l, 1931- P. J. CARLISLE 1,801,412

PROCESS FOR TREATING AND`RECTIFYING VAPORS Filed Nov. 25, 1927--caaL//vq ATTORNEY Patented Apr. 21, 1931 UNITED STATES PATENT OFFICEPAUL JOHNSON CARLISLE, or NIAGARA FALLS, NRW YORK, AssIeNoR, RY MESNEAS- sIeNMnNrs, To THR RORssLER & IIAssLACIIER CHEMICAL COMPANY, or NEWYORK, N. Y., A CORPORATION or DELAWARE .YPROCESS FOR 'JI'IBEIATIII'GVAND RECTIFYING VAPORS Application filed November 25, 1927. Serial No.235,503.

This invention relates to the treatment of vapors and especiallyhydrocarbon vapors. These hydrocarbons may be obtained from any source,such as the distillation of crude petroleum, cracking of hydrocarbons,hydrogenation of coal, distillation or extraction of oil shale, casinghead gasoline, etc. This invention is applicable to individualhydrocarbons as well as to mixtures.

These untreated products are usually undesirable for use because of thepresence of substances such as certain sulphur compounds and unstablehydrocarbons which have an unpleasant odor, which resinify on standing,etc. Thus in gasoline for motor use those undesirables must be reducedto render the product stable and saleable. In the succeeding specicationmy invention will be particularly described with reference to what iscommonly known as gasoline, but I do not Wish to be limited theretosince my invention is applicable to the treatment ot' hydrocarbons ingeneral. Indeed, the process is not limited to hydrocarbons since it maybe used wherever the simultaneous rectification and treatment of vaporsis desired.

The treating of crude gasoline usually results in the formation ofcertain solid and liquid by-products which may be polymers ofunsaturated compounds in the gasoline or may be compounds of thetreating agent with certain constituents of the gasoline, or both. Ingeneral, such by-products are troublesome since they tend to foul thetreating apparatus and the treating agent. In many cases it is necessaryfor economic reasons to recover the treating agent from its mixture withthe by-products; this, of course, adds an extra operation, and may beattended with considerable difficulty and expense. This prohibits theuse of relatively expensive treating agents even though they produce asuperior product. Thus, for example, sucli difiiculties form one of theprincipal reasons Why alkali metals have not been used to any greatextent commercially in treating crude gasolincs even though it is knownthat the treated product is of excellent quality.

Gasolines of high quality can be produced by contacting crude gasolinevapors with a treating medium consisting of alkali metal in llquidhydrocarbon, removing a part of the treated gasoline as vapors and partas liquid, thev latter serving to remove the treatnient by-products, insolution, in suspenson or both. The liquid portion can then be treatedVby such processes as distillation for recovery of its gasoline content.

The object of this invention is to provide a process for treating vaporscomprising subjecting vapors undergoing rectification to the action of atreating agent in the reflux liquid, said agent and liquid flowing incounter current to the vapors undergoing rectification and removing thetreated rectitied vapors by Way of the reflux means and removing thetreatment by-products with the higher-boiling liquid effluent. Aspecifi,- object is to provide a process for treating gasoline vaporsfrom cracking processes and rpm straight run distillations of crudo o1s.

The accompanyinor drawing illustrates diagramatically one iPorm ofapparatus suitable for applying the principles of this invention.

Lower boiling hydrocarbons consisting of those fractions commonlydesignated as gasoline and kerosene together with any wild, i. e., stillmore volatile gases are passed as vapors by way of pipe 1 into adistilling column 2 at a suitable point 3. The column is provided with areiux condenser, 4, and with a heating coil, 5.

Vessel Swicontains treating agent and is equipped with an agitator 7 andwith heating means not shown. Opening 8 is used for introducing alkalimetal and pipe 9 for introducing liquid hydrocarbon. A flowmeter 10 fortreating agent which is introduced by Way of pipe 11 into one of theupper sections of the column, is provided.

The treated and distilled gasoline leaves the column by way of pipe 12,as vapor and upon condensation is ready for use.

The liiger boiling liquid hydrocarbons together with the treatmentby-produets How downward through the column and leave the column by pipe13. This eiuent can be passed to a separating means such as a filter ora centrifuge and the clarified liquid disposed of in any desired way;for example, it can be cracked.

There are many Ways in which alkali metal may be introduced into thecolumn. Thus, it may be introduced as a stream of molten metal, as acolloidal suspenslon, as finely divided solid metal, or in any othersuitable form. One method of making and applying colloidal sodiumconsists inpassin a condensed electric spark between two so 'umelectrodes placed at a suitable distance from each other under a liquidsuch as ether, xylene, etc. Such a colloidal suspension is thenintroduced directly into the column.

I prefer to distribute the alkali metal in liquid hydrocarbon outside ofthe column and to introduce this mixture into the column. This mixturemay be prepared in vessel 6 by introducing alkali metal and liquidhydrocarbon and suitably agitating the mixture at a temperaturepreferably above the melting point of the alkali metal. A measured rateof the mixture is introduced into one of the sections at a suflicientdistance above the inlet for the hyrocarbon vapors to be treated andrectified so as to insure sufficient treatment and a satisfactory degreeof utilization of the alkali metal.

In most cases it is desirable to confine as largely as possible thetreating action to the hydrocarbons which leave the column as vapors. Todo this the alkali metal should be fed at such a rate that substantiallall of it is utilized in the upper part o the column. Therefore thealkali metal sho-uld not be fed at an excessive rate. To this end it isalso an advantage to have the alkali metal as finely subdivided aspossible.

In order to avoid ambiguity and a multiplicity of claims, the followingdefinitions of the terms used in the claims and specification are heregiven: The term alkali metal covers these metals, i. e., sodium,potassium, etc., singly or in various combinations or mixtures with eachother or with other metals such as calcium, magnesium, mercury, lead,tin, etc., in any applicable physical state. The term by-products coversall of the substances that are formed in the treating medium and thatare not removed with the treated hydrocarbon vapors leaving therectifier. The term hydrocarbons stands for mineral oils, gasolines, andany other hydrocarbon materials that may be improved by such treatmentas herein described. The term reflux liquid covers the liquid componentin a rectifier, traveling counter current to the flow of vapor. The

term rectifier obviously includes any device suited for rectificationsuch as a plate column, a s1eve column, a packed tower, etc.

that said alkali metal is substantially completely reacted between thepoint of its introduction and the vapor inlet; removing a portion of thetreated hydrocarbon as` and refiuxing sufficient of said vapor; treatedhydrocarbon to suspend said alkali metal, and by its fiow tosubstantially completely remove contaminating by-products from thesurface of the alkali metal and from the rectifying means.

2. The process of treating vapors comprising subjecting hydrocarbonvapors undergoing rectification to the action of sodium in the refluxliquid, said sodium and liquid fiowing in counter current to the vaporsundergoing rectification at such rate that said sodium is substantiallycompletely reacted between the point of its introduction and the vaporinlet; removing a portion of the treated hydrocarbon as vapor; andrefluxing sufficient of said treated hydrocarbon to suspend said sodium,and by its How to substantially completely remove contaminatingby-products from the surface of the sodium and from the rectifyingmeans.

3. The treating process comprising passing freshly vaporizedhydrocarbons from a cracking process into a rectifier in counter currentIto a treating medium consisting of alkali metal in refluxed liquidhydrocarbon at such rate that said alkali metal is substantiallycompletely reacted between the point of its introduction and the vaporinlet; removing a portion of the treated hydrocarbon as vapor; andrefluxing sufficient of said treated hydrocarbon to suspend said alkalimetal, and by its flow to substantially completely* remove contaminatingby-products from the surface of the alkali metal and from the rectifyingmeans and removing treated hydrocarbon vapors of the desired boilingrange.

4. The process of treating hydrocarbon vapors comprising subjectinghydrocarbon vaporsI undergoing rectification to the action of finelydivided sodium in the reflux liquid, said sodium and liquid flowingcounter current to the vapors undergoing rectification and removing thetreated, rectified vapors by Way of the reflux means and removin thetreatment by-produets with the higherboiling liquid effluent.

5. The process of treating hydrocarbon vapors comprising subjectinghydrocarbon vapors undergoing rectification to the action of colloidalsodium in the refiux liquid, said sodium and liquid flowing countercurrent Vat such rate that said alkali metal is substantially completelyreacted between Ythe point of its introduction and the vapor inlet tothe rectifying means, removin treated and rectified vapors by way of t ereflux means and removing the treatment by-products with the liquidefiiuent from the rectifying means.

Signed at Niagara Falls, in the county of Niagara and State of New York,this 19 day of November A. D. 1927.

PAUL JHNsoN CARLISLE.

CERTIFICATE OF CORRECTION.

Patent No. 1, 801, 412.

Granted April 21, 193,1, to

PAUL JOHNSON CARLISLE.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction a claim 4. and page 3,lines 2 to 5, claim 5,

s follows: lPage 2, lines 122 to 125, strike out the words .'andremoving the treated, reectified vapors by way of the reflux means andremoving the treatment bil-products with the higher boiling liquideffluent" and insert instead at Y such rate that said sodium issubstantially lof its introduction and the vapor inlet; removi carbon asvapor; and refluxing sufficient of sai completely reacted between thepoint ng a portion of the treated hydrod treated hydrocarbon to suspendsaid sodium, and by its flow to substantially completely removecontaminating by-products from the surface of the sodium and from therectifying means; and that the said Letters Patent should be read withthese correction therein that the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 4th day of August, A. D. 1931.

(Seal) Wm. A. Kinnan, Acting` Commissioner of Patents.

